JPS60181121A - Epoxy resin composition - Google Patents

Abstract

Curable compositions comprising substituted bisurea catalyzed epoxide prepolymers alone, or with aromatic polyamine curing agents, alone, or in further combination with reinforcements, e.g., graphite fibers, and optionally modified with second resins are disclosed. The cured resin fiber matrix compositions exhibit high toughness combined with excellent hot wet strength.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to improved epoxy resin compositions. The present invention further relates to curable epoxy resin compositions comprising reinforcing filaments and epoxy prepolymers cured with a series of converted bisurea catalysts derived from aryl monoisocyanates and diamines, alone or in combination with aromatic polyamines. .

Epoxy resin compositions are useful in the encapsulation of electronic components, as structural adhesives, and the like. Reinforced epoxy resin compositions with high strength-to-weight ratios find numerous applications in the aircraft and space industries and in other areas where strength, corrosion resistance, and light weight are desirable. For example, fiber resin matrix materials are replacing aluminum and other metals in the primary and secondary structures of modern military and commercial aircraft. Sports equipment such as tennis rackets and golf clubs have also successfully employed fiber resin materials.

Epoxy resin compositions and fiber modifying agents are abundant. Since the advent of fiber resin matrix materials, much effort has been devoted to improving their properties and properties, including the development of many curing systems.

Adding to such epoxy compositions curing agents such as substituted ureas and boron trifluoride-amine complexes that act as accelerators or catalysts to cure them, and also meeting the curing temperature of such resin systems. It is known to reduce the Substituted ureas made from monoamines and polyinocyanates and used for this purpose are described, for example, in U.S. Pat.
No. 79, the use of boron trifluoride-amine complexes is also described and claimed in the latter.

Although such curing agents reduce gluing time, they tend to reduce the mechanical properties of high performance epoxy resins, especially those containing tetraglycidyldiaminodiphenylmethane. It also increases the toughness of the resin, but reduces the thermal/market properties and glass transition temperature.

Amine and polyamine hardeners are widely accepted for use with epoxies alone or in combination with substituted urea hardeners or boron trifluoride-amine complexes. These include, for example, polyamides, aromatic compounds such as di-phenylenediamine, 4.4L diaminodiphenylmethane and 3°3'-diaminodiphenylsulfone, as well as British Patent No. 1,184,377, U.S. Pat. No. 3,9
No. 34360 and Gillham, Organic.
Coatings and Applied Poly
mer 5science proceedings.

Mention may be made of the aminobenzoates described in Vol. 45, pp. 592-598, March-April 1982. Such aromatic polyamines are effective as curing agents for various polyperoxides, and the resulting cured compositions are useful as films, moldings, coatings, and glass reinforced laminates. The properties presented in the past art generally do not demonstrate that the curing agents exemplified therein provide the combination of toughness and strength under the requisite thermal/market conditions when used in the structural applications described above. Related Patent No. 518,879, referenced above, discloses a thermoset composition comprising an epoxy prepolymer and a novel class of aromatic polyamine curing agents, I? A fiber resin matrix is described that includes reinforcing filaments in a resin composition. This patent describes pure resin formulations that have modified physical properties after curing, such as high extensibility and satisfactory thermal/market modulus. Furthermore, the filament-cured and catalyzed epoxy composition exhibits improved interlayer toughness and post-impact residual compressive strength while maintaining compressive strength under hot/market conditions.

We now demonstrate that a special Class I bisurea catalyst can be prepared by reacting aryl lemon isocyanates with organic diamines, and that its use in epoxies, alone or in combination with polyamines, provides desirable temperature-viscosity trends during curing. It has been discovered that unexpected resistance to deterioration in properties during heat/market conditions as well as retention of thermal properties is provided.

According to the invention, (α) an epoxy prepolymer or a combination of prepolymers having as many as 91 epoxide groups per molecule, and (b) (+) a reaction product of an aryl monoincyanate and an organic diamine. an effective amount of a bisurea compound to cure the epoxy, alone or together with (?+) (ii) an effective amount of an amine-functional aromatic curing agent to cure the epoxy; A thermosetting composition is provided.

Such compositions are suitable for adhesives, potting
ing) compounds, encapsulating resins, molding resins, coatings, etc.

Also provided are such compositions in combination with fiber reinforcing agents and modified resins. That is, an A0 reinforced filament and B, (a) an epoxy brepolymer or a combination of a brepolymer having one more epoxide group per molecule, and (b) a reaction product of (i) an aryl monoisocyanate and an organic diamine. alone or together with (b) (ii) an effective amount of an amine-functional aromatic amine curing agent to cure the epoxy; (C) component (C) in an amount sufficient to enhance toughness and resistance to aging under thermal/rational stress conditions in composites made from the composition. a) , (bXi) and (b)(ii
) and a second homogeneous or heterogeneous resin component blended and alloyed with a thermosetting epoxy resin composition.

The resins of type (C) can be present homogeneously or even in what is known as an inter-penetrating polymer network.

Preferably, in such compositions, the epoxy sol polymer in the thermosetting epoxy has a high io oz part, the bisurea hardener has 0.25 to 20 parts by weight, and the amine-functional aromatic amine hardener has io to 20 parts by weight. 55 parts by weight, and the second homogeneous or heterogeneous resin component is 5 to 50 parts by weight per total ttloO parts by weight of the thermosetting epoxy resin composition.

A preferred series of promoters (6)(i) according to the invention are of the formula [
In the formula, X is a divalent organic hydrocarbon group, a divalent or trivalent heteroatom-mediated hydrocarbon group, or a divalent inertly substituted hydrocarbon group; a hydrocarbon group, an amino or hydrocarbon-substituted amine group, a cyanide group, a hydrocarboxy group or an inertly substituted such group, and R1 is independently hydrogen, a monovalent hydrocarbon group; group, inertly substituted hydrocarbon group, single bond, or 2
a valent alkylene group or an inertly substituted such radical.

Particularly preferred examples include a divalent alkylene group having 2 to 12 carbon atoms, a trivalent nitrogen-interposed alkylene group having 4 to 12 carbon atoms, a divalent arylene or polyarylene group having 6 to 12 carbon atoms. Or -CR2-, -0- having 6 to 30 carbon atoms
, -5- or -5o2- group intervening divalent polyarylene group 1, where R2 is hydrogen, a monovalent hydrocarbon group or an inertly substituted hydrocarbon group, R is hydrogen, Cyan, amino, methoxy, vinyl or ethynyl, and R' is hydrogen, alkyl having 1 to 6 carbon atoms, and 6 to 6 carbon atoms
The bisurea of the above formula is an aryl of 12 or a divalent alkylene having 2 to 3 carbon atoms.

Particular mention is made of the most preferred bisureas.

These are divalent alkylene with 2 to 12 carbon atoms, alkylene with 4 to 12 carbon atoms and trivalent nitrogen, carbon
With diaryl sulfone number 12 to 20! ,! l)
, R is hydrogen, amine, vinyl, methoxy or ethynyl, and R1 is hydrogen, alkyl having 1 to 6 carbon atoms, or divalent alkylene having 2 to 3 carbon atoms.

FIG. 1 is a schematic diagram of one method for manufacturing a fiber resin matrix prepreg tape of the present invention, and FIG. 2 is a schematic diagram of one method for manufacturing a fiber resin matrix prepreg tape of the present invention. FIG. 3 is an enlarged cross-sectional view of a strip of tape.

The curing catalyst of the present invention is prepared by reacting an aryl inocyanate with a diamine in a solvent such as toluene, acetonitrile or tetrahydrofuran, according to the following formula.

The reaction conditions are not particularly stringent. At least 2 moles of incyanate are used per mole of diamine. The temperature may be ambient temperature, for example 20-25°C, or may be gently heated to 100°C.

The reaction takes a relatively short time, usually one hour is appropriate.

The product is recovered in conventional manner, usually by precipitation, filtration and drying. It is usually obtained as a white crystalline solid and can be further purified if desired by conventional methods, for example by recrystallization.

Starting materials are commercially available or can be easily prepared. Aryl monoisocyanates that can be used include phenyl isocyanate, 4-methylphenylisocyanate, 4-methoxy/phenylisocyanate, 4-
Acetaminophenyl isocyanate 4-), 4-cyanophenyl isocyanate, 4-vinyl phenyl isocyanate, 4-ethynyl phenyl isocyanate, 4-isoproynyl phenyl isocyanate, 1-s7tyl isocyanate, 4-phenyl isocyanate, these 2 −
and 3-substituted isomers. Preferably phenyl isocyanate is used.

Similarly, diamines are available from many commercial sources and can be readily manufactured by those skilled in the art. These include di-1, di-2 and mixed di-1 and di-2 amines. Examples are ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1゜12-dodecamethylenediamine, N,N' -dimethylethylenediamine, N,N'-diethyl-1,3
-propanediamine, jetanolamine, N.

N'-dimethylethanolamine, piperazine, N-(
2-aminoethyl)piperazine, etc.

Preferred diamines are N,N'-dimethyl-1,6-hexamethylenediamine, N,N'-diethyl-1°3-propane-diamine, piperazine, N-(2-aminoethyl)piperazine and 1,3 -gulononediamine.

Generally, the resin compositions of the present invention are prepared by mixing a polyepoxide compound with a bisurea catalyst (6Xi) in an amount of, for example, 0.1 to 5 parts MD of 100 Keio parts of epoxide. If polyamine (b)(ii) is included, it is present in the usual quantitative ratios, e.g. 0.3 to 3 oNH-equivalents to 1 epoxide equivalent, preferably 1.0
~ & ON11-equivalents, and particularly preferably 1.5 ~ λ
Added in a ratio of 5NB-equivalents.

Mixing is carried out by heating at any time until a melt is obtained, e.g.
It is carried out at a temperature in the range from ~160°C, preferably from 80 to 140°C, and stirring is continued for a further few minutes. This melt is then poured into molds and heated for example at 135°C for 2 hours and then at 18°C.
A cast product is manufactured by reacting at 0° C. for 3 hours. The castings are then cut into coupons and tested. It has outstanding flexibility and thermal properties. The NE-equivalent here is the amount of aromatic polyamine in number 9 in which there are 1 g of hydrogen atoms bonded to the amine nitrogen.

Fillers, pigments, dyes, reinforcing materials such as glass fibers or non-woven fabrics, plasticizers and mixtures thereof are added to the epoxy resin-bisurea catalyst composition in known manner before the reaction in order to improve the final properties. be able to. Trowel coloring,
Application by brushing, wet or dip coating, spraying or other convenient methods may also be carried out.

The fiber resin matrix composition according to the present invention embeds filaments, such as glass fibers and/or non-stone filaments, in a curable resin composition to produce a fiber resin matrix that can be used and cured in solid composites.

filament material, epoxy sol polymer, curing agent and thermoplastic resin, and optional ingredients such as fillers, dyes,
Particular selection of processing aids, etc. can provide a range of curable compositions that are not previously known in the art and exhibit improved physical properties relative to known materials.

Glass filaments useful in the present invention are well known.

The non-quartz filament component may be any non-glass, non-silicon dioxide-containing material that improves the strength or other physical properties of the curable epoxy resin component (among others mentioned above).

Such filaments include carbon, graphite, silicon carbide, boron, aramid, polyester, polyamide,
rayon, polybenzimidazole, polybenzothiazole, such filaments with metal coatings, such as graphite fibers and filaments with nickel coatings and/or silver coatings, or combinations of such filaments. It is not limited to. Fibers (woven or non-woven) of such filaments, tows or mats or tapes (non-woven flat bundles of non-uniformly oriented filaments) may also be used if desired.

For applications requiring high toughness-to-weight ratio or shear strength, carbon fibers, graphite filaments, polyaramid filaments or nickel-plated graphite filaments are most suitable as disclosed in related patent application no. 358.637. suitable.

Epoxy resins suitable for the present invention are compounds having more than 91 epoxide groups per molecule that react with the primary and secondary polyamines of the present invention. Such epoxif 0
The repolymer contains polyhydric phenols such as hyalocatecol; resorcinol; hydroquinone; 4,4/-dihydroxydiphenylmethane; 4,4/-dihydroxy-3,3'-dimethyldiphenylmethane;4,4/-dihydroxydiphenylmethane;
-dihydroxydiphenyldimethylmecun;4,4'-
Dihydroxydiphenylmethylmethane: 4.4ξdihydroxydiphenylcyclohexane i4,4'-dihydroxy-3,a'-dimethyldiphenylpropane; 4,
4'-dihydroxydiphenyl sulfone or il:)IJ
polyglycidyl ethers of chlorinated and brominated products of the diphenols mentioned above; aldehydes of novolacs (i.e. monohydric or polyhydric phenols, in the presence of acid catalysts, Polyglycidyl ethers of diphenols obtained by esterifying 2 moles of the sodium salt of aromatic hydroxycarboxylic acids with 1 L/1 mole of dihalodane alkane or dino-rogundialkyl ether (in particular, the reaction product with formaldehyde); glycidyl ether (British Patent No. 1.017.612); .02
4.288), but is not limited thereto.

Other suitable compounds are aromatic amines and epichlorohydrin such as S, #/-diglycidyl-aniline; N, N
-dimethyl-N,N'-diglycidyl-4,4/-diaminodiphenylmethane; N,N.

, y /, ) y /-tetraglycidyl-4,4'-
Diaminodiphenylmethane; and N-diglycidyl-4
- Based on aminophenyl glycidyl ether, polyester, I? Contains xyl compounds. Particular mention may be made of N,N,N',N'-tetrag+) cisyl-i,a-zolopyrene bis(4-aminobenzoate).

glycidyl esters and/or epoxycyclohexyl esters of aromatic, aliphatic and alicyclic polycarboxylic acids,
For example, glycidyl esters of the reaction products of diglycidyl phthalate and diglycidyl adipate and 1 mol of aromatic or alicyclic dicarboxylic acid anhydride and 1 mol of diol or polyol having n hydroxyl groups, or optionally substituted with methyl groups. Hexahydrophthalic acid diglycidyl ester is also suitable.

Polyhydric alcohol such as 1,4-butanediol; 1.4
-butynediol; glycerol; i, i.

1-) IJ Methylol Pronogne; Glycidyl ethers of pentaerythritol and polyethylene glycol can also be used. Also suitable are triglycidyl isocyanate; and polycricidyl thioethers of polyhydric thiols such as bismercaptomethylbenzene; and diglycidyl trimethylene sulfone.

Preferably, the epoxy prepolymer component has the formula [wherein C
is 2, 3 or 4 and is equal to the valence of Q; Q is divalent; trivalent or tetravalent group; G is -0-, -NR/
- or -N-; R is hydrogen or alkyl; and d is 1 or 2 depending on the valence of G] and halogen- and alkyl-substituted derivatives of such compounds. be done.

Wa, □□,, Yatsi, 85 Yu, Arald□~-720
(Ciba-Geigy) (Dow Chem, 1
A compound of the formula commercially available as EPON 828 (Shell), a compound of the formula commercially available as EPON@1031 (5hett), and a compound of the formula [where Y is 1 or 2, X is 10- or -N-, R8 is H or C11, and n is 2-8
] contains the compound.

In the last compound of the above formula, the compound where X is 10- is Do
It is commercially available as a mixture from Chemical Company 1 under the sieve product name DEN-438.

Triglycidyl ethers of meta- and nogular hydroxyanilines of the formula are also suitable, for example. These are Cib
a-Geigy Product Name ARALD/TE
■It is commercially available as osoo and osto.

Generally, any of the polyamine aromatic compounds commonly used to cure such epoxide prepolymers can be used in the present invention. For example m- and p-phenylene diamine, diamino naphthalene, 4.
4'-diaminodiphenyl methane, 4+4'-diaminodiphenyl sulfone, 3.3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, etc. can be used.

Among these, 3,3ξdiaminodiphenyl sulfone is preferred.

For compositions comprising component (b)(ii), a particularly suitable series of polyamine curing agents has the formula A valent or trivalent organic hydrocarbon, a hydrocarbon containing a petro atom, a calendar hydrocarbon group, or -N-. They are for example British Patent No. 1,182.
They may be prepared from the corresponding starting materials, such as nitro compounds, by reduction according to the method described in No. 377. Additionally, U.S. Pat. 9 shows nine N-methylation methods.

Suitable aromatic polyamine curing agents (b)(ii) are those in which R is hydrogen, C1-C3 alkyl or phenyl;
is (1)-((J7.)'-(where V is an integer from 2 to 12),-((-"IL('ILO("H-(:ILOC
E-CIl,)-.

CM.

(where n and m are the same or different integers of 1 to 4), a group with a valence α selected from be.

Suitable curing agents have the formula: where 2 is an integer from 2 to 12, preferably from 2 to 6; In the formula, Y is -C'll, CH, OCE, C1i, OC
E, C1l, -.

However, 2 is an integer from 2 to 12, preferably from 2 to 6.] belongs to.

In the most preferred compounds, the primary diamine has the formula:
) Hair 1 is hydrogen or CI-C, alkyl such as methyl, and 2 is from 2 to 12, preferably from 2 to 6, most preferably from 3. It is also contemplated that such compounds may be used in conjunction with other conventional polyamines such as methylene dianiline, phenylene diamine, and the like.

m) The IJ Tsuknu resin composition should include a resin modifier in an amount sufficient to impart improved mechanical properties, particularly toughness, while retaining substantial resistance to degradation under thermal/market conditions. It becomes advantageous. Such resins can be present in homogeneous form and in what is known as interpenetrating polymer networks. Particularly useful in this regard are polyether resins derived from bisphenol A and engineered chlorohydrin and containing repeating units of the formula and reaction products of bisphenol A and substituted phthalic anhydride, followed by m-phenylene diamine It is a polyetherimide resin containing units of the formula (where n is a sufficient number to provide a molecular weight in the range of 20.000 to 60.000).

95 to 30, preferably 10 to 20 parts by weight per 100 parts by weight of the epoxy prepolymer can be used.

Such polymers are respectively Union Carbid
e company (Danbury, C'T, USA) under the trade name PKHH resin, and also as General E.
electrical company (Fair-field, CT)
(USA) under the trade name ULTEM resin. Their use in epoxy systems is described in the aforementioned patent application Ser. No. 518,879.

Other resins that can be used as thermoplastic modifiers include reactive and non-reactive butadiene-styrene-acrylonitrile core-shell modifiers, polyurethanes, nylons, carboxylated acrylonitrile-butadiene elastomers, such as the US Patent No. 3, 8
No. 94,113 and elsewhere. These generally have molecular weights in the range 5,000 to 60,000 and are used in amounts as described above.

One method of making the fiber matrix composition of the present invention is illustrated in the drawing. As can be seen in FIG.
yeboαrd) 4 and 6 to the pressure roller combination section 8. The resin composition can be applied from ordinary film coating application 12 to release paper 1
The layer 10 is coated onto a substrate such as 4 and passed through the pressure roller assembly 8. A release paper 16 is also supplied to the pressure roller combination section 8 .

The pressure roller 8 is set at a temperature and pressure that embeds the fibers 2 into the resin layer 10 to form a fiber matrix composition 18. In practice, fiber resin Presoleg tape 18 is manufactured at temperatures in the range of 190°F and
A condition of 1000 pounds of pressure on 5 inch centers is suitable.

Fibers 2, substrate 14 of resin layer 10, and release paper 16 are fed to pressure roller 8 and passed at a speed of 5 to 20 feet per minute.

The feeding of fibers 2 and resin layer IO to pressure roller 8 is selected to produce a fiber matrix of about 20-60% by weight resin and about 8-40% by weight fibers. For example, 120 strands of carbon fiber 6, 12 inches wide, are fed to pressure roller 8 with a resin layer of 0.009 to 0.0013 pounds per square foot. Obtained fiber resin ma)
IJ Lux 8 has a generally parallel fiber arrangement as shown in FIG.

Fillers, pigments, dyes, and other such as conventional additives and processing aids can be added to the fiber matrix compositions of the present invention prior to curing to affect the properties of the final resin composite.

The following examples illustrate how to practice the invention. This is given for illustrative purposes and is not intended to limit the invention.

The following method was used to prepare and cure the pure resin composition: melt the epoxy doblepolymer and incubate with bisurea at 100°C.
and mixed for 10 minutes. When using a polyamine, heat the epoxide doble polymer and polyamine component at 135°C.
The mixture was mixed for 10 minutes, cooled to 100° C., the bisurea catalyst was incorporated, and the mixture was degassed for 10 minutes. The liquid resin was then poured into the mold and heated at 135°C for 2 hours and at 180°C for 3 hours.
Allowed to cure for hours. The properties were determined on coupons cut from the castings using the following method: bending tests were performed using ASTM
D-790, Law 1. Dynamic mechanical analysis was performed on an IJ) rbpont 981 dynamic mechanical analyzer, with Tg defined as the temperature at which the tangent of extinction tαnσ is maximum. The ASTM D4065 method covers this type of Tg measurement. The state before the test is based on "market conditions" and "
Described with the word "dry". "Market condition" means conditioned for two weeks at 71°C while soaking in distilled water prior to testing at 93°C. “Drying” means drying the sample in its manufactured state.
Means tested at 3°C.

Examples 1-6 A series of substituted bisureas were prepared by stirring a solution of phenyl isocyanate and the corresponding diamine in acetonitrile for 0.5 to 2.0 hours and separating by p-filtration. The reactants used and the products obtained are listed in Table 1.

Examples 7 and 8 Epoxy prepolymer, catalyst of Example 2 alone and 2
providing a composition comprising together with two different diamines;
The gluing time was measured isothermally at 180°C. For comparison purposes, the bisurea catalyst of Example 1 of US Pat. No. 3,386,955 was also used.

The formulations used and the results obtained are shown in Table 2.

Examples 9-13 A general method was used to produce pure resin compositions using two catalysts according to the invention. For comparison purposes, catalyst-free cured compositions as well as conventional bisurea-catalyzed versions were prepared. The formulations used and the properties obtained are shown in Table 3.

\ The deterioration in strength and thermal properties caused by conventional catalysts was ameliorated by using the catalyst of the present invention.

Example 14 The pure resin method was modified by modifying it at 250"l" for 1.5 hours and the degree of cure was determined by differential calorimetry (DSC). The formulations used were as follows in parts by weight and 7'C
: N, N, N/, N/-tetraglycidyl-4,4'-') aminodiphenylmethane, 61; bisphenol A cidalisidyl ether, 39; m-diaminodiphenylsulfone, 4o; and phenyl isocyanate and n, N The reaction product of '-diethyl-1°3-progundiamine (Example 2), 7, had a degree of cure of 80% by DSC, indicating excellent potential catalytic activity.

Example 15 Two fiber resin matrix formulations were made from the following materials: Fiber ■ Component (a) ARALI) ITE MY 720EPO
N■1031 (Reference, above formula) Catalyst (b) (i) )
Reaction product of luene-2,4-diisocyanate with dimethylamine (control); of phenyl isocyanate,
Reaction product with N,N'-diethyl-1,3-7'lopanediamine (Example 2) (Curing agent) (bXii) Trimethylenebis-(p-
(aminobenzoate) Polymer modifier (C) Polyether alcohol (pKHH
) The apparatus generally shown in FIG. 1 was used to produce pregreg tapes having the structure generally shown in FIG. 2: Example Shade) Polymer Modifier*1 Catalyst (TI) I/DMA) Invention Example 2) *Comparative Example** Reaction product of bisphenol A and epichlorohydrin (Union Carbide, pKIII
).

These samples were cured and compared against a commercially available epoxy resin matrix. The resin sheets involved were as follows: quasi-isotropic: 167-) ((+45/o'/9
0) J# compressive strength, D, H, Woolsencra
ft et al., Composi-tea, 1981, 10
Mon, 275-280 Negatively Written Modified ASTM
Measurements were made on the D695 sample. The compressive strength after impact is
B, A, Byer8゜NASA Report CR1
No. 59293, August 1980. This property allows the cured laminate sample to be supported on a rigid substrate (e.g. &5 inch steel cutout).
The samples were tested by subjecting them to an impact of 1500 inch-pounds per inch of nominal thickness using a 0.62 diameter spherical tip impactor. The panels were then tested in compression. Results are not shown in Table 4: The data show that the reinforced cured composition of the present invention (Example 15) has lower hot/market compressive strength than the matrix composition containing the other two catalysts (1
5A).

Example 16 A resin composition was prepared by mixing (parts by weight): Nilmethane (formula above) (C) ) Rimethylenebis(7-amino 48 parts benzoate) Following the general method of Example 15, 35 to A pre-leg tape was made using a 45%, preferably 40%, 155% to 65%, preferably 60% resin fill. When this was formed into a laminate according to the method of Example 14, a composite of excellent quality was produced. Preferred ranges of the composition are (a) 94 to 126 parts; (6) 14.25 to 126 parts;
1575 parts i (C) 45.6 to 504 parts; and (0 of
．． It was 5 to 2.5 parts.

The patents, patent applications and publications mentioned above are incorporated herein by reference. It will be appreciated that the present invention produces products with beneficial properties that make them useful in a variety of applications.

Looking at the detailed description above, many changes will come to mind for those in the industry. All such obvious variations are intended to be included within the scope of the following claims.

[Brief explanation of the drawing]

FIG. 1 is a schematic illustration of one method for producing a fiber resin matrix prepreg tape of the present invention, and FIG. Enlarged cross-sectional views f, b of the strip of tape. Patent applicant: American Cyanamid Company Engraving of drawings (no change in content) FI6.2 Procedural amendment (method) % formula % 1. Indication of case 1985 Patent Application No. 21000 2. Name of invention Epoxy resin composition Item 3: Relationship with the case of the person making the amendment Patent applicant 4: Agent 〒107 Drawings

Claims (1)

Claims: 1. (α) an epoxy prepolymer or combination of prepolymers having more than one epoxide group per molecule;
and (6) (i) alone or (b) an amount of a bisurea compound effective to cure the epoxy comprising the reaction product of an aryl monoincyanate and an organic diamine; and (ii) cure the epoxy. an amine-functional aromatic curing agent in an amount effective to impart a thermally curable composition. λ The bisurea compound (6)(i) has the formula [wherein, X is a divalent organic hydrocarbon group, a divalent or trivalent heteroatom-mediated hydrocarbon group, or a divalent inert R is hydrogen, a monovalent hydrocarbon group, an amino or hydrocarbon-substituted amino group, a cyanide group, a hydrocarboxylic group, or an inertly substituted group; and R1 are independently hydrogen, a monovalent hydrocarbon group, an inertly substituted hydrocarbon group, a single bond, or a divalent alkylene group or an inertly substituted such group. A composition as claimed in claim 1. 3. In the bisurea compound (6) (+), X is a divalent alkylene group having 2 to 12 carbon atoms, or 4 to 12 carbon atoms.
Alkylene group with trivalent nitrogen intervening, carbon number 6-12
divalent arylene or polyarylene group, or -CR2-, -0- having 6 to 30 carbon atoms. -5- or -502- group intervening divalent polyarylene group, provided that R2 is hydrogen, a monovalent hydrocarbon group, or an inertly substituted hydrocarbon group, and R is hydrogen, cyan, amine, methoxy, vinyl or ethynyl, and R1 is hydrogen, alkyl having 1 to 6 carbon atoms, or 6 to 1 carbon atoms;
The composition as claimed in claim 2, which is an aryl of 2 or a divalent alkylene having 2 to 3 carbon atoms. 4. In the bisurea compound (b) (i), diarylsulfone, R is hydrogen, amino,
The boiled composition according to claim 3, wherein R1 is vinyl, methoxy or ethynyl, and R1 is hydrogen, alkyl having 1 to 6 carbon atoms, or divalent alkylene having 2 to 3 carbon atoms. . 5. The composition as claimed in claim 2, wherein in compound (b) (i), X is 1+C, R1 is -CH3, and R is -H. 6. In compound (bXi), X is -(CR2+-r
Ashi, R1 is -CM2CH, Ashi, and R is -
A composition as claimed in claim 2 which is B. 7. In compound (b) (i), X is one+CH2+
-r- and R and R1 are -R. 8. In the compound (bXi), X is -(C11 well), and R and R1 are -H. 9. In the compound (b) (1) , X is -(0M2), R is -H, one R1 is a single bond, and the other R1 is -(CB2)1-, and one end is a single bond. A composition as described in claim 2 of the appended claims. io, in compound (b)(i), X is a trivalent group -C112-C112-N -C112-C112-, and R is -B, one R1 is -H, and the other R1 is -(CR2-h-, one end of which is connected to N in the single bonded X) according to claim 2 Compositions such as.